Synthesis of naphthalene and indene precursors to naphthoic and indenoic acids

As part of ongoing research to investigate structural requirements for lactate dehydrogenase inhibition by highly substituted naphthoic and indenoic acids, certain naphthalene and indene precursors to those types of compounds are required. Described here are efficient preparations of 1-naphthoic acid precursors 6-benzyl-2,3-dimethoxy-1-propylnaphthalenes, including compounds with substituted benzyl groups and 7-benzyl-2,3-dimethoxy-1-propylnaphthalene. Also described are the syntheses of indenoic acid precursors 2-benzyl-5,6-dimethoxy-7-propyl-1H-indenes, including compounds with substituted benzyl groups. These compounds were made from the key intermediates 6,7-dimethoxy-5-propyl-1-tetralone, 6,7-dimethoxy-8-propyl-1-tetralone, and 5,6-dimethoxy-4-propyl-1-indanone.     

Crystallographic and magnetic structure of HAVAR under high-pressure using diamond anvil cell (DAC)

Annealed (H1) and cold-rolled (H2) HAVAR has been studied using high-pressure synchrotron X-ray diffraction. A structural phase transformation was discovered at ～13 GPa at ambient temperature, transforming from m ??3 m (S.G. 225) to P 63/m m c (S.G. 194) symmetry. The transition was not reversible on pressure release. The low-pressure cubic phase was found to be more compressible than the high-pressure hexagonal phase. Conventional Mössbauer and NFS shows that the HAVAR is not magnetic at room temperature and no splitting is observed. The SQUID indicates a huge difference in the temperature dependence of the magnetic susceptibility between the cold Rolled HAVAR compared to the annealed HAVAR.     

Effect of K+ ion on the dielectric properties of metallo organic L-alanine cadmium chloride single crystals

The single crystals of pure and Potassium doped L-alanine cadmium chloride (LACC), a metallo organic nonlinear optical material is grown by a slow evaporation technique. The grown crystals were confirmed by single crystal, powder XRD analyses and atomic absorption studies. Dielectric measurements were carried out for different frequencies at different temperatures. The dielectric constant decreases due to the introduction of large ionic radius K⁺ ion in the pure LACC crystal. The low dielectric constant and dielectric loss suggest that it can be used as inter-metal dielectric material.     

Reductive side of water splitting in artificial photosynthesis: new homogeneous photosystems of great activity and mechanistic insight

Rhodamine photosensitizers (PSs) substituting S or Se for O in the xanthene ring give turnover numbers (TONs) as high as 9000 for the generation of hydrogen via the reduction of water using [Co(III)(dmgH)(2)(py)Cl] (where dmgH = dimethylglyoximate and py = pyridine) as the catalyst and triethanolamine as the sacrificial electron donor. The turnover frequencies were 0, 1700, and 5500 mol H(2)/mol PS/h for O, S, and Se derivatives, respectively (Φ(H(2)) = 0%, 12.2%, and 32.8%, respectively), which correlates well with relative triplet yields estimated from quantum yields for singlet oxygen generation. Phosphorescence from the excited PS was quenched by the sacrificial electron donor. Fluorescence lifetimes were similar for the O- and S-containing rhodamines (～2.6 ns) and shorter for the Se analog (～0.1 ns). These data suggest a reaction pathway involving reductive quenching of the triplet excited state of the PS giving the reduced PS(-) that then transfers an electron to the Co catalyst. The longer-lived triplet state is necessary for effective bimolecular electron transfer. While the cobalt/rhodamine/triethanolamine system gives unprecedented yields of hydrogen for the photoreduction of water, mechanistic insights regarding the overall reaction pathway as well as system degradation offer significant guidance to developing even more stable and efficient photocatalytic systems.     

Sol hydrolysis and condensation reaction time influence the sensitivity of class II xerogel-based sensing materials

Simplicity of preparation, a wide variety of precursors, and numerous processing variables (e.g., pH, time, temperature) are often described as attractive aspects of sol–gel derived materials. In the current work we create a series of O₂-responsive xerogel-based sensor films by simultaneously co-hydrolyzing and co-condensing tetramethylorthosilane and n-octyltriethoxysilane. Tris(4,7′-diphenyl-1,10′-phenanthroline) ruthenium(II) ([Ru(dpp)₃]²⁺) is used as the O₂-responsive luminophore. We determine the effects of [Ru(dpp)₃]²⁺ addition time to the sol and the sol hydrolysis and condensation reaction time (H&C) on the xerogel film O₂ sensitivity. [Ru(dpp)₃]²⁺ addition time has no significant effect on the O₂ sensitivity; H&C effects the O₂ sensitivity. The highest O₂ sensitivity is seen at early H&C (0.5 h). This behavior arises because TMOS and C8-TMOS react at different rates to form sols. At early H&C the co-hydrolysis and co-condensation reactions are not complete and the so formed sols are rich in C8-TMOS in comparison to their composition at longer H&C. At longer H&C, the TMOS and C8-TMOS co-hydrolyze and co-condense more completely. SEM images show that xerogel films formed at early H&C is more porous in comparison to those formed a longer H&C. The results of these experiments: (a) highlight the importance of documenting how sols are processed and xerogels formed and (b) demonstrate the use of a single sol formulation and H&C to create suites of sensor materials with different responses.     

Time-resolved fluorescence spectroscopy for illuminating complex systems

Over the years, the emissive characteristics (spectral, temporal, and polarization) of fluorophores have been widely used to probe a wide variety of systems. Fluorescence lifetime and rotational reorientation time measurements, in particular, offer a means to elucidate key details about complex systems. Further, because fluorescence occurs on the nanosecond (10⁻⁹ s) timescale, competing or perturbing kinetic processes like collisional quenching, solvent relaxation, energy transfer, and rotational reorientation can affect the fluorescence and hence be quantified. Thus, a carefully chosen and “placed” fluorophore can serve as an reporter on a wide range of nanosecond or faster events. This contribution is divided into three sections. The Theory section discusses time-resolved anisotropy and intensity decay kinetics (time and frequency domains), pump–probe spectroscopy, and up-conversion. The second section describes time-correlated single photon counting (TCSPC) and multifrequency phase-modulation fluorescence instruments. The final section is divided into subsections on the use of time-resolved fluorescence: (1) to study solvation dynamics, biochemical systems, polymer photophysics, and organized media; (2) as a tool in the separation sciences, microscopy, and sensing; and (3) coupled with multiphoton excitation strategies.     

Narrow-line diode laser system for laser cooling of strontium atoms on the intercombination transition

We report a diode laser system developed for narrow-line cooling and trapping on the ¹S₀–³P₁ intercombination transition of neutral strontium atoms. Doppler cooling on this spin-forbidden transition with a line width of /2=7.1 kHz enables us to achieve sub-K temperatures in a two-step cooling process. The required reduction of the laser line width to the kHz level was achieved by locking the laser to a tunable Fabry–Pérot cavity. The long-term drift (>0.1 s) of the reference cavity was compensated by employing the saturated absorption signal obtained from Sr vapor in a heat pipe of novel design. We demonstrate the potential of the system by performing spectroscopy of Sr atoms confined to the Lamb–Dicke regime in a one-dimensional optical lattice. PACS 32.80.Pj; 39.30.+w; 42.55.Px     

Public channel cryptography by synchronization of neural networks and chaotic maps

Two different kinds of synchronization have been applied to cryptography: synchronization of chaotic maps by one common external signal and synchronization of neural networks by mutual learning. By combining these two mechanisms, where the external signal to the chaotic maps is synchronized by the nets, we construct a hybrid network which allows a secure generation of secret encryption keys over a public channel. The security with respect to attacks, recently proposed by Shamir et al., is increased by chaotic synchronization.     

Recoil-free spectroscopy of neutral Sr atoms in the Lamb-Dicke regime

Recoil-free as well as Doppler-free spectroscopy was demonstrated on the 1S0-3P1 transition of Sr atoms confined in a one-dimensional optical lattice. By investigating the wavelength and polarization dependence of the ac Stark shift acting on the 1S0 and 3P1(m(J)=0) states, we determined the wavelength where the Stark shifts for both states coincide. This Stark-free optical lattice, allowing the purturbation-free spectroscopy of trapped atoms, may keep neutral-atom based optical standards competitive with single-ion standards.